Composition comprising chlorinated butyl rubber, zinc oxide, and a curing aid, process for vulcanization thereof, and vulcanized product obtained thereby



U d S ate, Pe

COMPOSITION COMPRISING CHLORINATED :BUTYL RUBBER, ZINC OXIDE, AND A CURING AID, PROCESS FOR VULCANIZA- TION THEREOF, AND VULCANIZED PROD- UCT OBTAINED THEREBY P. Baldwin, Colonia, and Robert M. Thomas, Westfield, NJ., assignors to Esso Research and Engineering Company, a corporation of Delaware No Drawing. Application September 24, 1956 Serial No. 611,777

- 18 Claims. 01.152-330 This invention relates to the vulcanization of chlorinated rubbery copolymers of isoolefins and multiolefins, preferably chlorinated butyl rubber, and to the resulting compositions formed thereby. More particularly, the

present invention relates to curing chlorinated rubbery isoolefin-multiolefin copolymers in the substantial absence of added elemental sulfur by an admixture of at least one bivalent metal oxide, preferably zinc oxide, and certain thiuram sulfides and/or thiocarbamates.

The present invention is a continuation-in-part of US. patent application Serial No. 512,182, filed May 31, 1955 in names of Francis P. Baldwin and Robert M. Thomas and is also a continuation-in-part of application Serial No. 597,993, filed July 16, 1956 in the names of Francis P. Baldwin and Robert M. Thomas.

It is known that unmodified isoolefin-multiolefin rubbery copolymers or chlorinated isoolefin-multiolefin rub-' bery copolymers may be cured by heating the same at an elevated temperature in the presence of minor propor-. tions of a combination of curatives comprising an admixture of sulfur, zinc oxide, and thiuram sulfides and/or certain thiocarbamates. It has also been recently discovered that chlorinated isoolefin-multiolefin rubbery copolymers, such as disclosed and claimed in Serial No. 512,182, may be cured in the absence of added elemental sulfur by basic metal compounds which are advantageously bivalent metal oxides, of which zinc oxide is pre ferred. However, the zinc oxide type of cure for chlorinated isoolefin-multiolefin rubbery copolymers is not as rapid as obtained by the abovementioned combination of curatives, namely sulfur, zinc oxide and either thiuram sulfides or thiocarbamates.

Although unmodified isoolefin-multiolefin copolymers such as butyl rubber may be effectively vulcanized with the last-mentioned combination of curatives, it is also known that the omission of any one of the three components of the curative combination results in substantially no vulcanization. This is known to be the case particularly when sulfur is the component omitted.

In accordance with the present invention, it has now been found that chlorinated isoolefin-multiolefin rubbery copolymers and particularly chlorinated butyl rubber may be effectively cured solely by the combination of a bivalent metal oxide such as zinc oxide and a curing aid which is either a thiuram sulfide and/ or a thiocarbamate.

2,926,718 Patented Mar. 1, 1960 4 to parts by weight of zinc oxide and about 0.05 to In fact, the omission of the sulfur has surprisingly been i found not to cause any loss of benefits such as fast cure rate and further, has been found to result in a vulcanizate possessing improved dynamic fatigue resistance, i.e., de-

15.0, advantageously about 0.1 to 100, preferably about 0.1 to 4.0 parts by Weight of a curing aid such as a thiuram sulfide and/or a thiocarbamate. The resulting composition is then subsequently vulcanized, also in the substantial absence of added elemental sulfur, as more fully described hereinafter. More particularly, the above new and useful vulcanizable compositions are then cured in the substantial absence of added elemental sulfur at a temperature of from between about room temperature to about 450 F.,: advantageously between about 200 and 400 F., preferably between about 250 and 400-F. for

a periodof time of between about 0.05 minute up to about several hours or more, preferably for about 0.1,.

having outstanding dynamic fatigue resistance. I

It is a further discovery of the present invention that when chlorinated isoolefin-multiolefin rubbery copolymers particularly chlorinated butyl rubbers,.are covulcanized in accordance with the invention, with minor proportions, say about 0.5 to 30% by weight, preferably about 1 to 10% by weight based on total rubber of more highly unsaturated rubbers such as dienestyrene copolymers (GR-S rubber), natural rubber or the like; the re-' sulting compositions surprisingly exhibit both improved heat aging characteristics and ozone resistance compared to the values obtained when evaluating vulcanizates containing no highly unsaturated rubber.

The thiuram sulfides found particularly useful for the purposes of the present invention include, among others, C to C alkyl (or C to C aryl, aralkyl or alkaryl) thiuram sulfides such as tetramethyl thiuram monosulfide, tetramethyl thiuram disulfide, tetraethyl thiuram d isulfide, tetrabutyl thiuram disulfide, tetraamyl thiuram disulfide, di-N-pentamethylene thiuram tetrasulfide, tetraphenyl thiuram disulfide, tetrabenzyl thiuram disulfide, Ndimethyl-N-phenyl aminoethyl-N'-phenyl thiuram disulfide, mixtures thereof, etc.

The thiocarbamates found to be particularly useful for' the purposes of the present invention include, among others, such materials as metal or amine salts of thiocarbamic acids such as minute to about 5 hours, to give improved vulcanizatesj tellurium diethyl dithiocarbamate;

zinc dimethyl dithiocarbamate;

copper dimethyl dithiocarbamate; cadmium diamyl dithiocarbamate; zinc dibutyl dithiocarbamate; selenium dipropyl dithiocarbamate;

lead dimethyl dithiocarbamate;

potassium diethyl dithiocarbamate;

lead(-o-tolylaminoethyD-O-tolyl dimethyl dithiocarbamate;

zinc-N-pentamethylene dithiocarbamate;

zinc dibenzyl dithiocarbamate;

N-pentamethylene ammonium pentamethylene dithiocarbamate;

zinc (phenyl. aminoethyl) phenyl dimethyl dithiocarbamate;

mixtures thereof, et

It is also within the purview of the present invention to vulcanize about parts by weight of chlorinated isoolefin-multiolefin copolymers at an accelerated rate-in the substantial absence of added elemental sulfur, not only in the presence of a minor proportion, sufficientto improve dynamic fatigue resistance on flexing, of madmixture of a basic metal oxide such as zinc oxide and thiuram sulfides and/or thiocarbamates, but also with a about 0.01 to- 10, advantageously about 0.1 to 5.0, preferably about 0.2 to 3.0 parts by weight of accelerators containing combined sulfur. Typical accelerators include benzothiazyl disulfide,

mercaptobenzothiazole,

bis-4,5-dimethyl thiazyl disulfide,

zinc benzothiazyl sulfide,

dinitrophenyl benzothiazyl sulfide,

Z-mercaptothiazoline,

benzothiazyl-Z-monocyclohexyl sulfenamide,

benzyl hexamethylene tetraammoniumlZ-benzothiazyl sulfide,

Z-mercapto imidazoline,

phenyl aminomethyl-Z-benzothiagyl sulfide,

mixtures thereof, etc.

Also, theforegoing novel vulcanizable chlorinated rub; bery copolymer-containing compositions which are preferably chlorinated butyl rubber-containing compositions may-be blended with, prior to vulcanization, conventional amounts of carbon blacks, mineral fillers such as clays, silica, metal oxides, talc, diatomaceous earth, plasticizers, glycols, resins, organic esters, extender oils, anti-oxidants or the like. 7 V

The chlorinated rubbery isoolefin-multiolefin copolymers to be used may be made by mild chlorination of the synthetic rubber as more fully described hereinafter. The. synthetic rubber to be chlorinated is advantageously a high molecular weight copolymer of a major proportion of an isoolefin and a minor proportion of a multiolefin. Copolymers of the above general type, having Staudinger molecular weights between about 20,000 and 100,000 and iodine numbers of between about 0.5 and 50 (Wijs), especially where the copolymer contains about 85 to 99.5 weight percent of a C to C isoolefin such as isobutylene, Z-methyl-l-butene, 3-methyl-1-butene, or the like, with about 15 to 0.5 weight percent of a multiolefin of about 4 to 14, preferably about 4 to 6 carbon. atoms, are commonly referred toin patents and in technical literature as butyl rubber or GRI rubber (Government Rubber-isobutylene). For instance, the preparation and uses of butyl-type rubbers are described in US. Patent 2,356,128 to Thomas et al. and in the book Synthetic Rubber by G. S. Whitby. The rubber preferably comprises the reaction product of isobutylene with a conjugated diolefin such as isoprene, butadiene, dimethyl butadiene, piperylene or such multiolefins as cyclopentadiene, dicyclopentadiene, cyclohexadienes, dimethallyl, allo-ocymene, vinyl fulvenes, etc. The reaction product of isobutylene and isoprene is preferred.

The above-described rubber-ycopolymer, which is pref erably butyl rubber, is then chlorinated, as disclosed and claimed in Serial No. 512,182, in a manner which does not degrade the molecular weight thereof, but sulficiently to-produce a rubber which retains its tensile strength upon heat-aging. The chlorination is preferably carried out so as to make the resulting chlorinated butyl rubber contain about at least 0.5 weight percent (preferably at least about 1.0 weight percent) combined chlorine, but not more than about X weight percent combined chlorine wherein:

L mol e.percent of the multiolefinin the, polymer M molecular weight of the isoolefin,

olecular, weight of the multiolefin tonne w i h of. chlorine more than about one atom of combined chlorine per double bond in the polymer. Normally, the chlorine content of the chlorinated polymer should be within about 0.1 to 10.0 weight percent, preferably about 0.5 to 3.0 weight percent chlorine based on polymer.

Suitable chlorinating agents which may be, employed are molecular chlorine, alkali metal hypochlorites, sulfur chlorides, chlorohydantoins, pyridinium chloride perchloride, N-chlorosuccinimide, alpha-chloroacetoacetanilide, tri-chlorcphenol chloride, N-chloroacetamide, betachlor-methyl phthalimide and other common chlorinating agents. The preferred chlorinating agents are molecular chlorine and sulfuryl chloride.

The chlorination is conducted at temperatures of from above about 0 to about 100- C. and preferably at about 20 to C. for about one minute to several hours, the temperature and time being regulated to chlorinate the rubbery copolymer to the extent abovementioned. The pressure may vary from about 0.5 to 500 p.s.i.a., atmospheric pressure being satisfactory.

It has been found that at these chlorination conditions, for every chlorine atom combined with and retained in the polymer, one hydrogen atom evolves from thepolymer. When molecular chlorine, or compounds liberating molecular chlorine (at the reaction conditions) are used in the presence of substantially inert solvents, about one mole of HCl is liberated per mole of chlorine .consumed and per gram atom of chlorine retained in the polymer. When other chlorinating agents, containing one or more reactive chlorine atoms per mole in the form of combined chlorine are used, such as N-chloroacetamide, N- chlorosuccinimide, dimethyl dichloro-hydantoin, etc., at least some of the hydrogen atoms removed from the polymer (which amount to about one hydrogen atom per chlorine atom entering the polymer) may combine'with the residue of the chlorinating agent. These proportions of chlorine being combined with the polymer, and hydrogen being removed from the polymer, are a strong indication that the chlorination takes place essentially by hydrogen substitution.

Also, in the case of using molecular chlorine as the, chlorinating agent, and at the conditions stated above, it is highly preferable and in many. cases necessary (such as when employing elemental chlorine in a completely inert solvent and under conditions such that all of the chlorine is consumed.) to limit. the amount of chlorine present in the reaction mixture so as not substantially to exceed about 2 times. the amount of chlorine which will bev retained in the rubbery copolymer. If this amount of chlorine in the reaction mixture is substantially exceeded, more chlorine than one atom per double bond inthe polymer tends to enterthe. polymer causing rapid degradation thereof. In the case of less reactive chlorinating agents containing combined chlorine, the proportionof chlorine added to the reaction mixture may be a greater multiple of that retained in the. polymer, say from above about 2 to about 5 times that retained in the polymer, depending on the reactivity of the chlorinating agent so as to establish reasonable chlorination rates such as will not tend to substantially degrade the polymer. Also, obviously when chlorinating with 616? mental chlorine in a solvent medium capable of reaction with chlorine, higher concentrations of chlorine than about?. times thatwhich will be retained in the copolymer may be used; such concentrations depending on the relative reactivity and concentration of the solvent and polymer respectively, under the reaction conditions used.

The chlorination of the rubbery copolymer may be ac complished in various Ways. One process comprises preparing a solution of the copolymer-as above,,in a suit: able inert liquid organic solvent such as an inert hydrocarbon or advantageously halogenated; derivatives of saturated hydrocarbons, examples ofwhich are hexane, heptane, naphtha, kerosene, straight; run mineral spirits, hen; zene, toluene, naphthalene, chlorobenzene, chloroform,

sure may vary, depending upon the foregoing temperatures and times from about 1 to 250 p.s.i.a.

The concentration of the copolymer, such as butyl rubber, in the solvent will depend upon the type of reactor, molecular weight of the rubbery copolymer, etc. In general, the concentration of a butyl rubber having a viscosity average molecular weight of about 50,000 to about 2,000,000, preferably about 200,000 to about 1,000,000, if the solvent is asubstantially inert hydrocarbon, will be between about 1 and 80% by weight, pref.- erably about 5 to 40%. If chlorine gas is employed, it may also be diluted with up to about times its volume, preferably about 0.1 to 5.0 times its volume of an inert gas such as nitrogen, methane, ethane, carbon dioxide, etc'. .In the case of chlorinating butyl rubber with gaseous chlorine in batch procedure, the chlorine is preferably added relatively slowly (e.g., over a period of time of about 1 to minutes) to a preformed solution of the butyl rubber with agitation. For a continuous process; preformed butyl rubber in solution, and gaseous elemental chlorine are preferably contacted in an orifice mixing zone or preferably a multiple orifice mixing zone of any commercially available type wherein the butyl solution passes consecutively through a plurality of orifrees, the chlorine gas being advantageouslybubbled into the butyl rubber solution at one or more points. Alternatively, a plurality of agitated reaction zones in series may be employed, wherein the chlorine is added to the first zone, or the process staged, so asto increase the chlorine content in each zone to the final chlorine concentration desired.

The resulting chlorinated rubbery copolymer, such as butyl rubber, may be recovered in various manners. The copolymer may be precipitated with acetoneor an alcohol or any other known non-solvent for the rubber and dried under about 1 to 760 millimeters or higher of mercury pressure absolute, at temperatures of about 0 to 180 C., preferably about 50 to 150 C. (e.g., 70 C.). Other methods of recovering the chlorinated rubbery copolymer, from the hydrocarbon solution of the same, are by conventional spray or drum drying techniques. Alternatively, the chlorinated rubbery copolymer-containing solution may be injected into a vessel containing agitated water heated to a temperature sufficient to flash oil the hydrocarbon solvent and form an aqueous slurry of the rubbery chlorinated copolymer. This copolymer may then be separated from the slurry by filtration, dried and recovered as a crumb or as a dense sheet or slab by conventional milling and/or extruding procedures.

The chlorinated copolymer formed advantageously has a viscosity average molecular weight between about 250,000 and 2,000,000 (i.e., about 10,000 to 150,000 Staudinger) and a mole percent unsaturation between about 0.2 to 15.0, preferably about 0.5 to 5.0. The copolymer before curing may be further compounded with various fillers such as carbon blacks, clays, silica, or titanium. dioxide, etc., as well as with plasticizers which are preferably hydrocarbon plasticizer oils, antioxidants, resins, etc.

Q In order to more fully illustrate the present invention,

the following experimental data are given. 7

CHLORINATED BUTYL RUBBER A One run was made chlorinating butyl rubber. The butyl rubber employed was a commercial butyl rubber ducedby employing in thepolymerization feed about 2.5 weight percent isoprene and about 97.5% isobutylene. The butyl rubber had an eight minute Mooney viscosity at 212 F. of 71.0, a mole percent unsaturation of 1.47, a voscosity average molecular weight of 420,000, and contained about 0.25 weight percent based on rubber of N- lauroyl-p-amino phenol antioxidant.

The chlorination of a solution of the above uncured butyl rubber was conducted in a 1500-gallon glass-lined Pfaudler reactor, equipped with an agitator, baffle, submersed stainless steel sparger ring and a conduit leading a into said ring.

The solvent for the butyl rubber was as follows:

Component: Volume percent 2,2-dimethyl butane 0.1 2,3-dimethyl butane 2.40 Z-methyl pentane 10.75 3-methyl pentane 12.45 n-hexane ...;.......2;... i 44.85 Methyl cyclopentane 20.5

- 2,2-dimethyl-pentane 0.4 .Benzene 7.7 Cyclohexane 0.85

Gaseous chlorine was continuously added to the butyl rubber solution over a period of one-half hour at a temperature level of 30 C. and under about 25 p.s.i.g. pressure. The chlorine was added to the reactor through the conduit via the sparger ring which, as hereinbefore men: tioned, was immersed below the liquid level of the agitated butyl rubber solution. The chlorination was then terminated and the solution, containing the chlorinated butyl rubber formed, agitated for an additional ten minutes. The resulting solution of chlorinated butyl rubber was then water-washed three times to remove dissolved hydrogen chloride, the last water-wash containing enough NaOH to render the resulting wash-water neutral. There was then added to the solution 0.2 pound per pounds of chlorinated butyl rubber as a 10 weight percent solution in hexane of an antioxidant (2,6-di-tertiary butyl para cresol).

The absolute amounts of butyl rubber, solvent and gaseous chlorine added, as well as the calculated percent of added chlorine based on polymer and resulting percent The resulting water-washed solution containing the chlorinated rubbery butyl product A was then recovered by injecting the dissolved chlorinated polymer into an agitated aqueous solution containing a commercial wetting agent of the aliphatic poly oxyethyleue ether type (Stearox A. J.) in an amount of about 0.1 lb. per 100 lbs. of chlorinated rubber as a dispersing aid. The solution also contained about 0.5 lb. of zinc stcarate (an anti-tack agent) per 100 lbs. of chlorinated butyl rubber; the hot agitated aqueous solution containing 5,000 lbs. of water per 100 lbs. of chlorinated butyl rubber.

The agitated solution was maintained at a temperature of about F. whereby to flash oif the solvent and form an aqueous slurry of the chlorinated butyl rubber in water. This slurry was then filtered and chlorinated butyl rubber A, which was in the form of a wet crumb-,2 was fed to a dewatering extruder where the water content was reduced to about 5% by weight. The extrudate was then fed to a degassing extruding means where the water content was reduced to below 0.5% by corresponding to GR -I18 rubber. Such arubber is pro- 7 weight. The Mooney viscosity (8 minutes at 212 F.)

for the resulting chlorinated butyl rubber A (as finished) was 67.

Example 1 Two samples, each containing 100 parts by weight of chlorinated butyl rubber A were compounded on a cold rubber mill with 1 part by weight of stearic acid, 50 parts by weight of HAF carbon black, 5 parts by weight of zinc oxide, 0.5 part by weight of an antioxidant known as 2,2-methylene-bis(4-methyl-6-tertiary butyl phenol) and 5 parts by weight of a hydrocarbon .plasticizer oil (Necton 60), as well as with the followingxamounts of tetramethyl thiuram disulfide (i.e., tuads):

Parts by Weight Samplel Sample 2 Tirade 1. 0

The Necton 60 hydrocarbon plasticizer oil is derived from a naphthenic base crude oil and has the following physical properties:

Property Employed General Range Specific Gravity 0. so 0. 8-0. 91 Flash Point, F. (open cup method)..- 445 300-550 Viscosity, SSU 100 F 510 50-1, 000 Viscosity, SSU 210 F--- 55 20-200 Iodine N o. (cg./g.) 16 0-30 The foregoing compounded chlorinated butyl rubber blends were then cured at 307 F. for the periods of time indicated hereinafter. The tensile strength (in p.s.i.), extension modulus at 300% elongation (in p.s.i.) and elon- The above data show that the cure rate, tensile strength and modulus of chlorinated butyl rubber, vulcanized in accordance with the invention in the absence of added elemental sulfur, but in the presence of a combination of zinc oxide and a tetramethyl thiuram sulfide, are all improved. More particularly, the cure in accordance with the present invention results in a much higher tensile strength and modulus Without significantly lowering the elongation.

. Two additional samples (i.e., samples 3 and 4) were compounded on a rubber mill. Sample 3 was compounded in the same manner as sample 1 above, whereas sample 4 was compounded in the same manner as sample 2. :These compounded chlorinated butyl rubber-contain ing compositions were then each cured for 45 minutes at 307 F. in order to 'vulcanize the same.

Each vulcanizate formed was then subjected to a very severe Goodrich Flexometer Test which is used for tire studies. This conventional test determines the stabiiity of the respective. vulcanizates under 'fiexingconditions. In the Goodrich Flexometer test, they static load was 89 p.s.i., the stroke in inches on, the flexometer was 0.25 inch at a frequency of 30 cycles/second and the. oven cylinders having inch diameter. The most significant data are the permanent set, dynamic drift and heat build-up (temperature rise). The results were as follows:

Goodrich Flexometer Data Sample 3 Sample 4 Temperature Rise, 0 38 21. Dynamic Drift, inches. 0.092 0.000. Permanent Set, Pereent 1.50. Appearance Blew out Excellent. Run Time, minutes 14 30,

The above data show that the presence of tetramethyl thiuram disulfide, in addition to zinc oxide, in a non-sulfur cure of chlorinated butyl rubber, results in much better dynamic fatigue resistance, as shown by the negligible dynamic drift and low permanent set of the vulcanizate cured in accordance with the present invention, compared to the vulcanizate not containing tetramethyl thiuram disulfide. This latter vulcanizate exhibited higher dynamic drift. The permanent set could not be measured since the sample blew out during testing due to the rapid rise in temperature.

Example II One hundred parts by weight of either chlorinated butyl rubber A or unmodified butyl rubber were compounded on a rubber mill into the following compositions:

The foregoing compounded chlorinated butyl rubber blends were then cured in a mold for 15 minutes at 307 F., the shape of each respective pad formed being 4 x 6 x 0.075". The following physical inspections were noted:

Property Sample Sample Sample A B C Tensile Strength p.s.i 2, 730 2,250 360 Modulus at 300 a Elong., p 1, 690 1, 290 50 Elongation, Percent 450 470 Shore A Hardness 61 55 The above data show that the chlorinated butyl rubber composition of sample A, compounded and cured in accordanoe with the present invention, exhibited superior tensil strength, modulus andShore hardness compared to either a chlorinated butyl rubber-sulfur-containing composition cured under the same conditions (sample B), or an unmodified butyl rubber (sample C) compounded the same as sample A (i.e., without sulfur) and also cured under the same conditions. Sample C did not effectively cure, i.e., did not result in a technically useful vulcanizate.

Example Ill The same general procedure employed as in Example I was repeated, except that several different types of cures were employed, as. indicated hereinafter. The Goodrich Flexometer test was likewise run in the same manner as in Example I, except as otherwise indicated.

The most significant data in this example were found to be .the dynamic drift, permanent set, and appearance of the slug after testing. It was found that the appear ance of the slug after the test is in accord with the quantitative behavior of the foregoing parameters. The

L9,? final percent dynamic compression recorded in these tests gives: good indication of how much deformation the slug was undergoing at the end of the test. The appearance of the slugs was compared by cutting the same open, inspecting and rating them as follows:

Broken through and delarninated 10 g The following types of cures were employed.

1:0; '5 {Ihe above-data showfthat chlorinated butylf-rubber cured in the absence of sulfur with the combinationbfi zinc oxide and tetramethyl thiuram disulfide (or zinc oxide and zinc dibutyl dithiocarbamate) in accordance ;with the present invention exhibited excellent dynamic drift (i.e., 0.4-0.5% compared with values between about 3.6 and 21.9% for other known cures). The permanent set of the vulcanizate produced in accordance with the present invention was also by far thenlowest compared to other known vulcanizates.

Examples IV-VII The same general procedure as in Example III was again repeated except that minor proportions of natural rubber (smoked sheets) or GR-S rubber were added to theunmodified butyl rubber or chlorinated butyl rubber TABLE I Cure No -4 1 2 2A 3 4 5 6 7 8 i 9 Chlorinated Butyl Rubber A 100 100 100 100 100 100 GR-I18. 100 100 100 GR-I-25. 100 2,2-methy1ene-bis(4-methyl-6-tertiary l I butyl phenol) 1 1 1 1- Steeric Acid a 1 1 1 0.5 1 0.5 0.5 0.5 0.5 Carbon Black (HAF Black) 50 50 50 .50 50 50 50 50 50 50 Zinc Oxide. j 5 5 5 5- 5 '5 5 5 5 Magnesium Oxide; 5 Tellurium diethyi dithiocarbamatn 2 2 2 1 Tetramethyl thiuram disuifide. 1 Zine clibutyl dithiocarbamate-. 1 Benzothlazyl distllfirla 4 4 Diethylene Triamine 2 Lead Dioxide (PbO 2 Red Lead (PbflO-l) 5 9 Quinone Dioxime (GMF) 2 1. 5 Dibenzo GMF v 6 TABLE II Recipe, Cured 45' at 307 F. Goodrich Flexometer, 30 Minutes, 100 0., 0.25 in. stroke, v 89 19.5.1. (15 lb. wt.) 32 c.p.s.

Dynamic Final Perma- Max. Minutes Sample No Rubber Cure Type of Cure Dri Dynamic nent Set, Temp. to Max. Rating No. v Percent Compres- Percent Rise,- Temp. of Slug sion 0.

Ex. III-4.4-.. 'Ohl or. 'Butyi 2 Zn0+Tetramethy1 Thiu- 0.4 9. 0 2.2 24 14 0 J1 Rubber A. ram de. Ex. III-b d 2!. Zn 0+Zinc dibutyi dithio- 0. 5 10. 0 2. 0 13 0 3 cerbamate 1 1i 22. 3 43. 4 8.9 l 50 17 9 3 S11lfur+tellurium diethyl 9.6 17.6 8.3 31 28 3 dithiooarbamate. 1 4 p-quinone dioxime.-. 14.9 31.3 20.6 35 12 7 5 di e thyiene triamine+ I 3. 6 i 36. 3 3 35 I 3 10+ 8 i 6 Su1iur+tellurium diethyl 11.8 19. 1 16.9 24 12 3 dithiocarbamate. p v i 7 Sulfur+te1iurium diethyl 12.1 16.2 18.0 20 12 2 dithioearbnmate. 8 p-quinone dioxime 11.4 26.4 9.5 36 10 4 9 p-quinone dioxime di- 21. 9 35. 6 21. 0 33 19 9 beuzoate. GRI18- 8 S+Zinc dibutyl dithio- 10.8 .7 17.4 31 22 J10+ oarbemate. 9 i 1 Faflodut is minutes (ow/301mm; tailed at it mun). Failed at 3 minutes (907307 Frcure failed at 9 mln.);

, Not measurable.

armament following physical inspections being noted: I 7

TABLE III Recipe, Cured 45@307 F. 'Goodrich Flexometer. 30 minutes, 100 0., 0.25 in.

' Stroke, 89 p.s.l. lb. wt.) 32 c.p.s.

' Final Max.

Cure Dynamic Percent Perma- Temp. Minutes Sample No. Rubber Type of Cure No. Dri Dynamic nent Set, Rise, toMax.

. Percent Compres- Percent *0. Temp.

slon 7 Ex. 1v Chlorlnated-Butyl-Rubber A-- zr pt t enamethyl thiuram 2 0.4 9.0 2.2 24' 14 s Ex.V 98 wt. percent, Chlorinated Butyl Rubber do 2 0.0 8.0 3.5 11

. A+2 wt. percent smoked sheet. I p

Ex, VI 98 wt. percent Chlorinated Butyl Rubber .do 2 0.0 8.5 3.6 26 22 A-l-Z'wt. percent GR-S. v I EX,VII 75 wt. percent Chlorinated Butyl Rubber ----d0 ...4 2 3.5 12.1 4.4 i2 13 A+25 wt. percent GR-S. m GR- -18 Sulfur+tellur1um diethyl 6 11.8 19.1 16.9 24 12 dithiocarbamate. n 98 wt. percent GRI18+2 wt. percent --.-do 6 20.2 27.9 17.4 25 9 smoked sheet. 0 98 wt. percent GRI18+2 wt. percent .....(10 6 19.8 26.4 18.3 11

GR-S. p Chlorinated Butyl Rubber A do 3 9.6 17.6 8.3 31 28 q 98 wt percent Chlorinated Butyl Rub. do 3 6.0 13.5 10.6 27 21 A+2% smoked sheet. V r 98 wt percent Chlorinated Butyl Rub. do 3 6 2 17.5 11.0 24 10 A"+ 2 wt. percent GR-S. a

The above data show that both the dynamic drift and permanent set of the covulcanizates produced in ac- Tenfifle Strength, cordance with the invention by curing chlorinated butyl Example posit o 5 gl ftg hgg t rubber with zinc oxide and tetramethyl thiuram disulfide, 35 at R) in the absence of elemental sulfur, are superior to. they dynamic drift and permanent set of-either unmod1fied g b t g B 1C1]i bb -tak" 1 830 w ercen orina e u y butyl rubber or chlorinated butyl rubber vulcanized by H Rubber A 2 Wt Percem other known curative systems. smoked sheets 1,370

98 wt. Percent Chlorinated Butyl 75RvlberPA" 20 Iferioegt gilt-ff 1, 370

. ercen 1 011118. e 11 Example Rubber A 25 wt. Percent smoked sheets 760 75 wt. Percent Chlorinated Butyl Another .two samples of chlorinated butyl rubber A b erA 25wt. Percent GR-S. 810

were compounded on a rubber mill into the following compositions Parts by Weight Component Sample Sample R S Chlorinated Butyl Rubber "A" 100 100 gaigion Black (HAF) 5(5) n Stearic A bid 1. 0 1 Tetram ethyl thiuram disulfide 1. 0 Antioxidant, i.e. 2,2-methylenc-bis(4-methyl-6- tert. butyl phenol) 1.0 1. 0

Each sample was pressed into a 6 x 6 x 0.075" pad at 200 F. for 3 minutes and then cured in open steam at 320 F. for 20 minutes. The cure in the absence of tetramethyl thiuram disulfide gave poor results whereas the cure in the presence of both tetramethyl thiurarn disulfide and zinc oxide gave excellent results.

Examples lX-XIII Five additional runs were made vulcanizing and heat aging chlorinated butyl rubber A or blends of chlorinated butyl rubber with natural rubber (smoked sheets) and GR-S rubber. The results were as follows when compounded as in Example VIII and vulcanized for minutes at 307 F.

The above data show that small amounts (e.g., 2% by weight) of GR-S or natural rubber actually improved the heat aging characteristics of chlorinated butyl rubber zinc oxide-tetramethyl thiuram disulfide vulcanizates in that higher tensile strengths were obtained without appreciable change in other stress-strain properties. Also, large amounts of GR$ or natural rubber (e.g., 25% by weight) do not adversely affect the heat aging of chlorinated butyl rubber.

Examples XI V-X VIII Various unmodified and chlorinated butyl rubber coniposltlons were compounded in accordance with one or the other of the following recipes:

The ozone resistance of each vulcanizate upon press curing at 307 F. was as. follows. The ozone resistance was measured after exposures of 0.25 X 0.075 in. dumpbells at 50% elongation in 0.2% ozone.

'0 2one Examples XIX to XX VII 1 ReSlStfl-BOB R1111 Component; lloi'muiiti liginulies 1 aion ea 1 a I y 5 In these tests, chlorinated butyl rubber was vulcanized Cure) by combinations of zinc oxide with various thiuram sul- E XIV Cm MB IR bb A T tides and thiocarbamates. In each test, 100 parts by x. orina e uty u er 76 EKXV Chlorinated BmylRubberuAn weight of chlorinated butyl rubber A were compound +2 7; natural rubber 'r 13s ed with 50 parts by weight of HAF carbon black, 1 g f gg ggg fifi i fff ti u 134 10 part by weight of stearic acid, 0.5 parts by weight of the EX. xv11 Chlo-inatedButy1tgbber' antioxidant, 2,2'-methylene-b1s(4-methyl-6-tert. butyl g5,,fi,;;3gl;f,, g 5- phenol), l0 parts by weight of Necton 60 hydrocarbon GE 25% Git-sat. 105 plasticizer 011, 5 parts by weight of zinc oxide and 1 jjgi5%?glgfff'fif: 3; part by weight of a modifier (i.e., a thiuram sulfide or Chlorinated Blityl' fii ubberfit" 15 a thiocarbamate). The particular modifier, as well as gq ifigggg g g g -5511 U 67 the tensile strength,(in p.s.i.), elongation (in percent) +2% GR-S U 66 and extension modulus at 300% elongation (in p.s.i.) for one or more cure times at 307 F. were as follows:

-TABLE IV 1 Cured 1 0 @307" F. Cured min. 307 F. Cured 40 min. 307 F. Example Modifier -No.

Tensile Elong. Modulus Tensile Elong. Modulus Tensile Elong. Modulus 300% 300% 300% Nrm Control 1,025 530 335 1, 400 450 005 1,705 305 1,105 Tetramethyl thiurarn 0150111415.- 19 2,470 435 1, 525 2, 430 305 1, 725 2, 445 350 1, 970 Tetramethyl thiuram monosulii 20 2, 255 420 1, 420 2, 310 355 1, 345 2, 200 325 1, 975 Lead dimethyldithiocarbamate- 21 2,220 330 1, 050 2,225 345 1,375 2, 315 325 2,005 Copper dimethyl dithiocarbama 22 2, 265 435 1, 355 2, 295 390 1, 595 2, 190 345 l, 890 zinc dibutyldithiocarbemate----- 23 2,100 420v 1,335 2,245 400 1,500 2,255 385 1,010 Tellurium diethyldithi0carbamate.. 24 2,120 390 1, 495 2, 300 375 1,745 2,310 370 1,780 Tetraethylthiuram dis 25 2,150 440 1,345 2, 345 1 420 1,540 2,235 355 1,700 Di-N-pentamethylene thiruam totrasulfldm. 25 2, 225 430 1, 475 2. 255 3515 1, 540 2, 450 300 1, 775 Bismuth dimeth dithioca amate 27 1,410 510 745 2,000 300 1,400 2,200 340 1,850 Lead (o-tolyl amino-ethyD-o-tolyl dimethyl dithiocarbamate 23 1,000 490 800 2,075 a 405 1,450 2,200 355 1,850 24-dinitrophenyl dimethyldithioearbamate 29 1,490 560 650 1,925 520 800 2,000 495 950 bl-pentamethyiene ammonium pentamethylene dithiocarbamate 30 1, 50 480 800 Not tested.

The above data show that conventional thiuram sulfides or thiocarbamates are eiiective for the purposes of the present invention in improving the sulfur-free cure of chlorinated butyl rubber with bivalent metal oxides such as zinc oxide.

Examples XXXI-XXXI V Various samples of chlorinated butyl rubber A were each compounded on a rubber mill with 50 parts by weight of EPC carbon black, 1' part by weight of stearic acid, 10 parts by weight of Nectonhydrocarbon plasticizer oil, 5 parts by weight of zinc oxide, 1 part by weight of tetramethyl thiuram disnlfide, and in some instances, a sulfur-containing accelerator (i.e., benzothiazyl disulfide) and/or an antioxidant. The amounts in parts by weight of these last-mentioned ingredients, as well as the physical properties of the vulcanizates, which had been cured at 307 F. forvarious periods of time, are shown below in Table V.

TABLE V Exam le XXXI XXXII. XXXIII XXXIV Accelerator, i.e.. Benzothiazyl disulfide 0 0 1 1 Antioxidant, i.e., 2,2-rnethyiene-bis i-methylfi-tertiary butyl phenol) 0 1 0 1 Cured 10 min 307 F.:

Tensile (p.s.i.) 1, 775 1, 725 2, 2, 250 Modulus 300% E. (p.s.i. 750 750 925 690 Elongation, percent 520 505 565 655 Cured 20 min. 307 F Tensile (p.s.i.)--' 2, 000 2,175 2, 485 '2, 450 0duiu @300%E (psi)...' 1,200 1,050 1,025 920 Elongation, percent 435 460 670 590 Cured 40 min, 307 F.:

Tensile (n.s.i.) "2....-- 2, 340 2, 270 2, 450 2, 550 Modulus 300% E. (13.81.)-.. 1,450 1, 500 1, 340 1,250 Elongation, percent .2 410 405 495 530 The above data show that the presence or absence of a conventional antioxidant doesnot preclude the benefits of the present invention. The data also show that the presence of a typical sulfur-containing accelerator (i.e., benzothiazyl disulfide) benefically increases both the tensile strength and elongation of the resulting vulcanizate cured in accordance with the present invention.

Additional runs were made in which chlorinated butyl rubber A was compounded again as above and, in two other instances (sample A and sample B), also with a small amount of added sulfur. The amounts in parts by weight of the ingredients added, as well as the Goodrich Flexometer data (obtained in accordance with Example I) and in all instances fora run time of 30 minutes, a load of 89 p.s.i. and a stroke of 0.25 inch), after a 45-minute cure at 307 F., were as shown below in Table VI.

or bladders, conveyor. belting, transmission belting, steam hose, electrical insulation, inner tubes, inner-tube-containing tires, blown sponge rubber, car window channel strips, proofed goods, general molded mechanical goods and other applications where butyl rubber, certain chloroalkadiene rubbery homopolymers or copolymers and other rubberlike polymers have utility as shown and described in Figures II to V and pages 27 to 30 of application Serial No. 597,993, filed July 16, 1956, the description of which is also hereby incorporated into the present application by reference.

' Resort may be had to modifications and variations of the specific embodiments of the invention disclosed herein without departing from the spirit of the invention or the scope of the appended claims.

What is claimed is:

1. A compositionwhich comprises about 100 parts by TABLE VI Examnle XXXI XXXII XXXIII .XXXIV Sample A Sample B Accelerator,i.e.,benzothiazyldlsulfide 1.0 1.0 1.0 V 1.0 I t ii a t 22' h 1 hi 4 n oxi an, i.e., -met yeues methyl-fi-tertiary but yl phenol) 1. 0 1. 0 1. 0 1. 0 Change in temperature 0.) 1 13 14 18 19 22 22 Permanent Set 1 2. 4 2.2 3. 7 4. 4- 11.4 13.2

1 Goodrich Flexometer data.

The above data show that the presence of even very small quantities of sulfur (e.g., 0.5 parts by weight per 100 parts by weight of chlorinated butyl rubber) such as in sample A, results in a considerably higher permanent set, which is disadvantageous.

Examples X X X VX LI weight of the reaction product of an isoolefin-multiolefin rubbery polymer with a' chlorinating agent, said reaction product containing at least about 0.5 weight percent chlorine on a basis of the total weight of the polymer but not more than about one combined atom of chlorine per double bond in said polymer; and a minor proportion, sufficient to improve dynamic fatigue resistance, of an admixture of about 0.5 to 50 parts by weight of zinc oxide and about 0.05 to 15 parts by weight of a modifying agent selected from the group consisting of thiuram sulfides,

thiocarbamates and mixtures thereof, said composition being free of added elemental sulfur.

2. A composition comprising a rubbery polymer having a Staudinger molecular weight above about 20,000,

comprising atoms of hydrogen, carbon, and chlorine, containing in its structure a major proportion of hydrocarbon TABLE V11 Example Control XXXV XXXVI XXXVII XXXVIII ,XXXIX XL XLI Tetramethyl thiuram disulfide, pphr 0 0. 1 0.3 1.0 2. 0 4.0 6. 0 8. 0 Cured 10 min 307 F E Tensile 1, 025 1, 345 1,850 2, 470 2, 430 I 1, 900 1, 460 1,400 335 645 980 1, 625 1, 175 825 725 700 Elongation 530 530 475 435 530 550 485 460 Cured 20 min. 307 F.: 1

Tensile 1, 490 1, 720 2, 095 2, 430 2, 475 2, 075 1, 800 1, 700 Modulus. 905 l, 020 l, 360 1, 795 1, 440' 1, 200 1, 000 1, 000 Elongation. 460 430 415 395 475 455 455 430 Cured 40 min. 307

Tensile 1, 705 1, 950 2, 260 2, 445 2, 520 2,300 2,010 1, 900 Modulus 1, 195 1, 140 1, 530 1, 970 1, 520 1, 350 1, 350 1, 350 Elongation 395 a 430 400 360 445 445 400 375 The above data show that the curing aids of the invention such as tetramethyl thiuram disulfide are efiective, for the purposes of the present invention, in concentrations of from at least about 0.1 to 8.0 parts by weight per 100 parts by weight of rubber. This. is. demonstrated by the higher tensile strength and modulus at 300% elongation exhibited by the vulcanizates' of Ex- 1 amples vXXXV to XLI, compared to the control.

The compositions comprising chlorinated isoolefinmultiolefin copolymers, vulcanized in accordance with the units derived by the polymerization of isoolefins containing about 4 to 14 carbon atoms, and also containing sufiicient units in which a pair of carbon atoms is linked by an-olefinic double bond that the mole percent unsaturation of the polymer is from about 0.5 to 50.0; said polymer containing at least 0.5 weight percent chlorine but not more than about one combined atom of chlorine per double bond in the polymer; 100 parts by weight of said polymer being in composition with about 0.5 to parts by Weight of zinc oxide and about 0.05 to 15 parts by weight of a modifying agent selected from the group con- .sisting' of thiuram sulfides, thiocarbamates, and mixtures thereof, said composition being free of added elemental sulfur.

3; A vulcanized composition comprising about parts by weight of a rubbery polymer having a Staudinger molecular weight of between about 20,000 and 150,000,

17 comprising atoms of hydrogen, carbon and chlorine, containing in its structure from about 85 to 99.5 weight percent of hydrocarbon units derived by the polymerization of an isoolefin containing about 4 to carbon atoms, and also containing sufficient atoms in which a pair of carbon atoms is linked by an olefinic double bond that the mole percent unsaturation of the polymer is from about 0.5 to 35, said polymer containing at least about 0.5

weight percent combined chlorine but not more than 1 about X weight percent combined chlorine wherein X equals:

and

L=mole percent of the multiolefin in the polymer M =molecular weight of the isoolefin M =molecular Weight of the multiolefin and 35.46=atomic weight of chlorine 6. Composition according to claim 3 in which the modifying agentis a thiuram sulfide.

7. Composition according to claim 3 in which the modifying agent is a thiocarbamate.

8. A vulcanized rubber composition comprising a copolymer comprising about 85 to 99.5 weight percent of a C to C isoolefin and about 15 to 0.5 Weight percent of a C to C multiolefin; said composition having combined therein at least about 0.5 weight percent chlorine on the basis of the total weight of copolymer but not more than about one atom of chlorine per double bond in said copolymer; said composition being in admixture with about 0.2 to 3.0 weight percent of a sulfur-containing accelerator, about 0.1 to 10.0 weight percent of a modifying agent selected from the group consisting of thiuram sulfides, thiocarbamates, and mixtures thereof and about 1 to 50 weight percent of zinc oxide; said composition being free of added elemental sulfur.

9. Composition according to claim 8 in which the modifying agent is a C to C tetraalkyl thiuram sulfide.

10. Composition according to claim 8 in which the modifying agent is a C to C tetraaryl thiuram sulfide.

11. Composition according to claim 8 in which the modifying agent is a C to C metal alkyl thiocarbamate.

12. Composition according to claim 8 in which the modifying agent is an amine salt of a C to C N-alkyl thiocarbamic acid.

13. Composition according to claim 8 in which the modifying agent is a nitro C C aryl' dialkyl dithiocarbamate.

14. In a process for vulcanizing rubbery chlorinated isoolefin-multiolefin copolymers, said copolymers containing at least 0.5 weight percent chlorine but not more than about one atom of chlorine per double bond in the copolymer, the improvement which comprises compounding about 100 parts by weight of said chlorinated copolymer with a minor proportion, sufficient to improve dynamic fatigue resistance, of an admixture of about 0.5

.to 50 parts by weight of zinc oxide and about 0.05 to 15 parts by Weight of a modifying agent selected from the group consisting of thiuram sulfides, thiocarbamates, and mixtures thereof, and curing the resulting mixture in the absence of added elemental sulfur at a temperature between about 200 and 450 F. for between about 0.5

minute and 5 hours.

15. Process according to claim 14 in which the chlorination is performed at a temperature between about 20 and about C., the vulcanization being at a temperature between about 250 and 400 F. in the presence of about 0.1 to 10.0 weightpercent, based on copolymer of an accelerator containing combined sulfur, said accelerator being other than thiuram sulfides and thiocarbamates.

16. A vulcanized chlorine-containing rubbery composition comprising a major amount of a blend of a minor proportion based on total rubber of a'high unsaturation rubber and the remainder of total rubber being a low unsaturation isoolefin-multiolefin-containing rubbery copolymer having a Wijs iodine number below about 50, about parts by weight of said copolyrner having combined therein at least about 0.5 weight percent chlorine but insufficient chlorine to substantially alter the molecular weight of said rubbery copolymer, and a minor amount, sufficient to improve dynamic fatigue resistance, of an admixture comprising about 0.5 to 50 parts by weight of zinc oxide and about 0.05 to 15 parts by weight of a modifying agent selected from the group consisting of thiuram sulfides, thiocarbarnates, and mixtures thereof, said composition being substantialy free of added elemental sulfur, said composition when vulcanized exhibiting improved ozone resistance.

l7. Composition according to claim 16 in which the high unsaturation rubber is present in an amount of about 0.5 to 30% by Weight based on total rubber and is se lected from the group consisting of diene-styrene copolymers, natural rubben'and mixtures thereof.

18. A process for improving the heat aging and ozone resistance of an isoolefin-rnultiolefin butyl rubber copolymer having a mole percent unsaturation between about 0.5 and 10.0 which has been chlorinated to contain at least 0.5 weight percent chlorine but not more than about one atom of chlorine per double bond in the copolymer, said process comprising in combination, producing an elemental sulfur-free blend of a major amount of a mixture of a major proportion of about 100 parts by weight of the chlorinated butyl rubber copolymer formed with a. minor proportion based on total rubber of a more highly unsaturated rubber having a mole percent unsatur-ation between above about 10 to about 100 and, per 100 parts by weight of total rubbers, about 0.5 to 50 parts by Weight of zinc oxide and about 0.05 to 15 parts by weight of a modifying agent selected from the group consisting of thiuram sulfides, thiocarbanrates and mixtures thereof and curing the resulting blend in the absence of added elemental sulfur at a temperature of about 200 to 450 F. for between about 0.05 minute and 5 hours.

References Cited in the file of this patent UNITED STATES PATENTS 

1. A COMPOSITION WHICH COMPRISED ABOUT 100 PARTS BY WEIGHT OF THE REACTION RODUCT OF AN ISOOLEFIN-MULTIOLEFIN TUBBERY POLYMER WITH A CHLORINATING AGENT, SAID REACTION PRODUCTION CONTAINING AT LEAST ABOUT 0.5 WEIGHT PERCENT CHLORINE ON A BASIS OF THE TOTAL WEIGHT OF THE POLYMER BUT NOT MORE THAN ABOUT ONE COMBINED ATOM OF CHLORINE PER DOUBLE BOND IN SAID POLYMER, AND A MINOR PROPORTION, SUFFICIENT TO IMPROVE DYNAMIC FATIGUE RESISTANCE, OF AN ADMIXTURE OF ABOUR 0.5 TO 50 PARTS BY WEIGHT OF ZINC OXIDE AND ABOUT 0.05 TO 15 PARTS BY WEIGHT OF A MODIFYING AGENT SELECTED FORM THE GROUP CONSISTING OF THIURAM SULFIDES, THIOCARBAMATES AND MIXTURES THEREOF, SAID COMPOSITION BEING FREE OF ADDED ELEMENTAL SULFUR. 